Compare the general characteristics of the first series of the transition metals with those of the second and third series metals in the respective vertical columns. Give special emphasis on the following points:
(i) electronic configurations,
(ii) oxidation states,
(iii) ionisation enthalpies, and
(iv) atomic sizes.
(i) In the 1st, 2nd and 3rd transition series, the 3d, 4d and 5dorbitals are respectively filled.
We know that elements in the same vertical column generally have similar electronic configurations.
In the first transition series, two elements show unusual electronic configurations:
Cr(24) = 3d5 4s1
Cu(29) = 3d10 4s1
Similarly, there are exceptions in the second transition series. These are:
Mo(42) = 4d5 5s1
Tc(43) = 4d6 5s1
Ru(44) = 4d7 5s1
Rh(45) = 4d8 5s1
Pd(46) = 4d10 5s0
Ag(47) = 4d10 5s1
There are some exceptions in the third transition series as well. These are:
W(74) = 5d4 6s2
Pt(78) = 5d9 6s1
Au(79) = 5d10 6s1
As a result of these exceptions, it happens many times that the electronic configurations of the elements present in the same group are dissimilar.
(ii) In each of the three transition series the number of oxidation states shown by the elements is the maximum in the middle and the minimum at the extreme ends.
However, +2 and +3 oxidation states are quite stable for all elements present in the first transition series. All metals present in the first transition series form stable compounds in the +2 and +3 oxidation states. The stability of the +2 and +3 oxidation states decreases in the second and the third transition series, wherein higher oxidation states are more important.
For example are stable complexes, but no such complexes are known for the second and third transition series such as Mo, W, Rh, In. They form complexes in which their oxidation states are high. For example: WCl6, ReF7, RuO4, etc.
(iii) In each of the three transition series, the first ionisation enthalpy increases from left to right. However, there are some exceptions. The first ionisation enthalpies of the third transition series are higher than those of the first and second transition series. This occurs due to the poor shielding effect of 4felectrons in the third transition series.
Certain elements in the second transition series have higher first ionisation enthalpies than elements corresponding to the same vertical column in the first transition series. There are also elements in the 2nd transition series whose first ionisation enthalpies are lower than those of the elements corresponding to the same vertical column in the 1st transition series.
(iv) Atomic size generally decreases from left to right across a period. Now, among the three transition series, atomic sizes of the elements in the second transition series are greater than those of the elements corresponding to the same vertical column in the first transition series. However, the atomic sizes of the elements in the third transition series are virtually the same as those of the corresponding members in the second transition series. This is due to lanthanoid contraction.
Explain why Cu+ ion is not stable in aqueous solutions?
Silver atom has completely filled d orbitals (4d10) in its ground state. How can you say that it is a transition element?
The Eθ(M2+/M) value for copper is positive (+0.34V). What is possibly the reason for this? (Hint: consider its high ΔaHV and low ΔhydHV)
How would you account for the following:
(i) Of the d4 species, Cr2+ is strongly reducing while manganese (III) is strongly oxidising.
(ii) Cobalt (II) is stable in aqueous solution but in the presence of complexing reagents it is easily oxidised.
(iii) The d1 configuration is very unstable in ions.
Actinoid contraction is greater from element to element than lanthanoid contraction. Why?
Which is a stronger reducing agent Cr2+ or Fe2+ and why?
Explain giving reasons:
(i) Transition metals and many of their compounds show paramagnetic behaviour.
(ii) The enthalpies of atomisation of the transition metals are high.
(iii) The transition metals generally form coloured compounds.
(iv) Transition metals and their many compounds act as good catalyst.
Give examples and suggest reasons for the following features of the transition metal chemistry:
(i)The lowest oxide of transition metal is basic, the highest is amphoteric/acidic.
(ii)A transition metal exhibits highest oxidation state in oxides and fluorides.
(iii) The highest oxidation state is exhibited in oxoanions of a metal.
Predict which of the following will be coloured in aqueous solution?
Ti3+, V3+, Cu+, Sc3+, Mn2+, Fe3+ and Co2+.
Give reasons for each.
Describe the preparation of potassium dichromate from iron chromite ore. What is the effect of increasing pH on a solution of potassium dichromate?
For the reaction R → P, the concentration of a reactant changes from 0.03 M to 0.02 M in 25 minutes. Calculate the average rate of reaction using units of time both in minutes and seconds.
Write the formulas for the following coordination compounds:
(i) Tetraamminediaquacobalt (III) chloride
(ii) Potassium tetracyanonickelate(II)
(iii) Tris(ethane-1,2-diamine) chromium(III) chloride
(iv) Amminebromidochloridonitrito-N-platinate(II)
(v) Dichloridobis(ethane-1,2-diamine)platinum(IV) nitrate
(vi) Iron(III) hexacyanoferrate(II)
(i) Write structures of different isomeric amines corresponding to the molecular formula, C4H11N
(ii) Write IUPAC names of all the isomers.
(iii) What type of isomerism is exhibited by different pairs of amines?
Why are solids rigid?
Write any two characteristics of Chemisorption.
Write the structures of the following compounds.
(i) α-Methoxypropionaldehyde
(ii) 3-Hydroxybutanal
(iii) 2-Hydroxycyclopentane carbaldehyde
(iv) 4-Oxopentanal
(v) Di-sec-butyl ketone
(vi) 4-Fluoroacetophenone
Which of the ores mentioned in Table 6.1 can be concentrated by magnetic separation method?
Why are pentahalides more covalent than trihalides?
Glucose or sucrose are soluble in water but cyclohexane or benzene (simple six membered ring compounds) are insoluble in water. Explain.
Write structures of the following compounds:
(i) 2-Chloro-3-methylpentane
(ii) 1-Chloro-4-ethylcyclohexane
(iii) 4-tert. Butyl-3-iodoheptane
(iv) 1,4-Dibromobut-2-ene
(v) 1-Bromo-4-sec. butyl-2-methylbenzene
Name the following halides according to IUPAC system and classify them as alkyl, allyl, benzyl (primary, secondary, tertiary), vinyl or aryl halides:
(i) (CH3)2CHCH(Cl)CH3
(ii) CH3CH2CH(CH3)CH(C2H5)Cl
(iii) CH3CH2C(CH3)2CH2I
(iv) (CH3)3CCH2CH(Br)C6H5
(v) CH3CH(CH3)CH(Br)CH3
(vi) CH3C(C2H5)2CH2Br
(vii) CH3C(Cl)(C2H5)CH2CH3
(viii) CH3CH=C(Cl)CH2CH(CH3)2
(ix) CH3CH=CHC(Br)(CH3)2
(x) p-ClC6H4CH2CH(CH3)2
(xi) m-ClCH2C6H4CH2C(CH3)3
(xii) o-Br-C6H4CH(CH3)CH2CH3
Discuss briefly giving an example in each case the role of coordination compounds in:
(i) biological system
(ii) medicinal chemistry
(iii) analytical chemistry
(iv) extraction/metallurgy of metals
What are monosaccharides?
Write structural formulas and names of four possible aldol condensation products from propanal and butanal. In each case, indicate which aldehyde acts as nucleophile and which as electrophile.
List the important sources of sulphur.
Three electrolytic cells A,B,C containing solutions of ZnSO4, AgNO3 and CuSO4, respectively are connected in series. A steady current of 1.5 amperes was passed through them until 1.45 g of silver deposited at the cathode of cell B. How long did the current flow? What mass of copper and zinc were deposited?
What are lyophilic and lyophobic sols? Give one example of each type. Why are hydrophobic sols easily coagulated?
In terms of band theory, what is the difference
(i) Between a conductor and an insulator
(ii) Between a conductor and a semiconductor
Write the formulas for the following coordination compounds:
(i) Tetraamminediaquacobalt (III) chloride
(ii) Potassium tetracyanonickelate(II)
(iii) Tris(ethane-1,2-diamine) chromium(III) chloride
(iv) Amminebromidochloridonitrito-N-platinate(II)
(v) Dichloridobis(ethane-1,2-diamine)platinum(IV) nitrate
(vi) Iron(III) hexacyanoferrate(II)
Discuss the effect of pressure and temperature on the adsorption of gases on solids.